3-substituted - 2 - trifluoromethylacryloyl fluorides and the process for their preparation

ABSTRACT

DESCRIBED ARE SUBSTITUTED TRIFLUOROMETHYLACRYLOYL FLUORIDES HAVING A 3-SUBSTITUENT SELECTED FROM DIALKYLAMINO ARYLALKYLAMINO, ARYL, 5-MEMBERED RING AROMATIC HETEROCYCLICS HAVING AN ADDITION TO ONE OR MORE CARBON ATOMS THE FOLLOWING RING MEMBERS: OXYGEN, SULFUR, IMINO, ALKYLIMINO, OXYGEN AND UP TO 3 NITROGENS, SULFUR AND UP TO 3 NITROGENS, IMINO AND UP TO 3 NITROGENS, AND ALKYLIMINO AND UP TO 3 NITROGENS, BENZO-5-MEMBERED RING AROMATIC HETEROCYCLICS HAVING ADDITION TO ONE OR MORE CARBON ATOMS THE FOLLOWING RING MEMBERS: OXYGEN, SULFUR, IMINO, ALKYLIMINO, OXYGEN AND NITROGEN, SULFUR AND NITROGEN, IMINO AND NITROGEN, AND ALKYLIMINO AND NITROGEN. THE HETEROCYCLIC SUBSTITUENTS ARE BONDED TO THE TRIFLUOROMETHLYACRYLOYL FLUORIDE MOIETY BY A CARBON-CARBON BOND. THE CLAIMED PROCESS FOR THEIR PREPARATION COMPRISES THE REACTION OF A FORMYL-CONTAINING COMPOUND WITH PERFLUOROMETHACRYLYL FLUORIDE AT TEMPERATURES OF 0-200*C. 3-SUBSTITUTED-2-TRIFLUOROMETHYLACRYLOYL FLUORIDES ARE USEFUL AS TREATING AGENTS FOR PAPER PRODUCTS AND FABRICS.

United States Patent Oflice I 3,585,235 3-SUBSTITUTED 2 TRIFLUOROMETHYL-ACRYLOYL FLUORIDES AND THE PROCESS FOR THEIR PREPARATION David C.England and Leonard Solomon, Wilmington,

Del., assignors to E. I. du Pont de Nemours and Company, Wilmington,Del. No Drawing. Filed Feb. 28, 1967, Ser. No. 619,162 Int. Cl. C07c51/58, 63/00 U.S. Cl. 260-544 10 Claims ABSTRACT OF THE DISCLOSUREDescribed are substituted trifluoromethylacryloyl fluorides having a3-substituent selected from dialkylamino arylalkylamino, aryl,5-membered ring aromatic heterocyclics having in addition to one or morecarbon atoms the following ring members: oxygen, sulfur, imino,alkylimino, oxygen and up to 3 nitrogens, sulfur and up to 3 nitrogens,imino and up to 3 nitrogens, and alkylimino and up to 3 nitrogens,benzo-S-membered ring aromatic heterocyclics having in addition to oneor more carbon atoms the following ring members: oxygen, sulfur, imino,alkylimino, oxygen and nitrogen, sulfur and nitrogen, imino andnitrogen, and alkylimino and nitrogen. The heterocyclic substituents arebonded to the trifluoromethylacryloyl fluoride moiety by a carbon-carbonbond. The claimed process for their preparation comprises the reac tionof a formyl-containing compound with perfluoromethacrylyl fluoride attemperatures of 200 C. 3-substituted-Z-trifluoromethylacryloyl fluoridesare useful as treating agents for paper products and fabrics.

BACKGROUND OF THE INVENTION This invention relates to substitutedflUOfiIlfittEd-otficonjugated unsaturated carboxylic acid fluorides andto the process for their preparation.

Y .n u u, t

wherein Y is selected from the group consisting of O, S, and NR, R isselected from the group consisting of hydrogen and lower alkyl, one'Y YY or Y is C and the other Y Y Y and Y are selected from the groupconsisting of CH and N with the proviso that when four of Y, Y Y Y and Ycontain N, R is lower alkyl; Y? or Y is C,and the other Y or Y is CH orN;

' (c) 'RfR"N. where R is selected from tthe group consisting of loweralkyl and cycloalkyl and R" is selected 3,585,235 Patented June 15, 1971from the group consisting of lower alkyl and phenyl; and (d) CH=CH ingagents for various papers and cellulosi materials. Some of the compoundsare also useful as dyes.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The compounds of this inventionare prepared by the reaction of perfluoromethacrylyl fluorides with aformyl compound, i.e., aldehydes and substituted formamides, accordingto the equation The reaction of the formyl compound withperfluoromethacrylyl fluoride can be exothermic when the formyl compoundis electron rich such as N,N-dimethylform amide orp-N,N-dimethylaminobenzaldehyde. The exothermic reaction takes placereadily at room temperature and depending upon quantities of thereactants used can require cooling to moderate the reaction. Other lessreactive formyl compounds, such as furfural and benzaldehyde, do notproduce an exothermic reaction and require heating in order to effectreaction. Compounds of this latter type can be conveniently used in theprocess at temperatures of about -15() C. and above. Some product isproduced at lower temperatures when the less reactive formyl ompoundsare used.

The process for preparing the compounds of this invention can beconducted by mixing the reactants neat. It is also convenient especiallywhen the reactants produce an exothermic reaction, to moderate theprocess by adding the formyl reactants to perfluoromethacrylyl fluoride.The time required for addition of the formyl reactants can vary from afew minutes to several hours.

The molar ratio of the reactants ZCHO and perfluoromethacrylyl fluoridewhich can be brought together to carry out the reaction of thisinvention can be varied widely, i.e., from 10:1 to 1:10 respectively.Best yields of prodnets are obtained when the formyl compound andperfluoromethacrylyl fluoride are respectively employed in the molarratios in the range from 2:1 to 1:1.

The process of this invention can be carried out either in the presenceor in the absence of additives, such as diluents or solvents. It isconvenient to add a liquid reaction medium which is inert to thereactants and products. Such inert reaction media can be aromatichydrocarbons such as benzene, toluene, xylene, and the like; ethers suchas dimethyl ether, diethyl ether, and the like; or halocarbons such aschloroform, carbon tetrachloride, perchloroethylene, and the like.

Pressure is not critical in the process of this invention and pressuresboth above and below atmospheric pressure can be used. When temperaturesabove the boiling point of the reactants and/or reaction media areemployed, it is convenient to operate in a closed system underautogenous pressure.

To minimize side reactions between the by-product COF and the formylcompound ZCHO, it is convenient, though not essential, to provide forremoval of the byproduct, from the reaction mixture as it is formed.Removal can be effected by the use of partial or selective condensing ofthe reactants in reactions conducted under reflux.

Time of the reaction is not critical in the process embodiment of thisinvention. The length of time can be readily controlled by the choice ofthe reaction temperature. Reaction time for reactions having very fastrates can be dependent upon contact time and very short periods of time(i.e., one second to minutes) are operable. For reactions having slowerrates of reaction, the time required for reaction can be a matter ofabout 1 hour or less to three or four days or longer depending upon thereaction conditions used.

Recovery and isolation of the product of this invention from thereaction mixture can be carried out by known methods of evaporation,distillation, sublimation and crystallization. For example, in someprocesses using reactants in equimolar ratios, it suffices to vent theCOF by-product and obtain the reaction product in a slightly impure butusable form. Other conventional recovery methods, such as distillationor recrystallization or combinations of these recovery methods can beused.

R, R and R defined above, preferably contain 1-6 carbons including suchradicals as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,t-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, cyclopropyl,cyclobutyl, cyclopentyl and cyclohexyl. R and R" are also preferablyhydrogen and phenyl, respectively.

The multi-ring aryl hydrocarbon groups preferably contain 14 carbonatoms such as biphenyl, u-napthyl, B- naphthyl, l-anthracyl andl-phenanthryl.

The compounds of this invention wherein Z is a heterocyclic group areproduced by the reaction of perfiuoromethacrylyl fluoride with anaromatic heterocyclic aldehyde. Examples of aromatic heterocyclicaldehydes useful in the process embodiment of this invention include:

furan2- and 3-carboxyaldehyde thiophene-2- and 3-carboxaldehydepyrrole-2- and 3-carboxaldehyde l-methylpyrrole-Z- and 3-carboxaldehydel-hexylpyrrole-2- and 3-carboxaldehyde l,2-oxazole-3-, 4- and5-carboxaldehyde 1,3-oxazole-2-, 4- and S-carboxaldehyde1,2-thiazole-3-, 4- and S-carboxaldehyde 1,3-thiazole-2-, 4- andS-carboxaldehyde 1,2-diazole-3- and 4-carboxaldehyde 1,3-diazole-2- and4-carboxaldehyde 1-rnethyl-1,2-diazole-3- and 4-carboxaldehyde1-hexyl-1,2-diazole-3- and 4-carboxaldehyde 1-methyl-1,3-diazole-2,4-and S-carboxaldehyde 1-hexyl-l,3-diazole-2,4- and S-carboxaldehyde1,3,4-oxadiazole-2-carboxaldehyde 1,3 ,4-thiadiazole-2-carboxaldehyde1,3,4-triazole-2-carboxaldehyde l-methyl-1,3,4-triazole-Z-carboxaldehydel-hexyl-l,3,4-triazole-2-carboxaldehyde 1,2,3-oxadiazole-4- andS-carboxaldehyde 1,2,3-thiadiazole-4- and S-carboxaldehydel,2,3-triazole-4-carboxaldehyde l-methyl-1,2,3-triazole-4- andS-carboxaldehyde 2-hexyl-1,2,3-triazole-4-carboxaldehyde 41,2,4-oxadiazole-3- and S-carboxaldehyde 1,2,4-thiadiazole-3- andS-carboxaldehyde l-methyl-1,2,4-triazole-3- and S-carboxaldehyde4-methyl-1,2,4-triazole-3-carboxaldehyde1,2,3,4-oxatriazole-5-carboxaldehyde1,2,3,4-thiatriazole-S-carboxaldehydel-ethyl-1,2,3,4-tetrazole-5-carboxaldehyde1,2,3,5-oxatriazole-4-carboxaldehyde1,2,3,S-thiatriazole-4-carboxaldehydel-methyl-l,2,3,4-tetrazole-5-carboxaldehydel-methyl-1,2,3,5-tetrazole-4-carboxaldehyde 1,2-benzofuran-3- and4-carboxaldehyde 2,3-benzofuran-Z-carboxaldehyde 1,2-benzothiophene-3-and 4-carboxaldehyde 2,3-benzothiophene-2-carboxaldehyde indole-2- and3-carboxa1dehyde l-methylindole-Z- and 3-carboxaldehyde l-hexylindole-Z-and 3-carboxaldehyde 2,3-benzopyrrole-2-carboxaldehyde4,5-benzo-1,2-oxazole-3-carboxaldehyde4,5-benzo-1,2-thiazole-3-carboxaldehyde4,5-benzo-1,2-diazole-3-carboxaldehydel-methyl-4,5-benzo-l,2-diazole-3-carboxaldehyde4,5-benzo-l,3-oxazole-2-carboxaldehyde4,5-benzo-1,3-thiazole-2-carboxaldehydel-methyl-4,5-benzo-1,3-diazole-2-carboxaldehyde Othern-alkyl-substituted heterocyclic aldehydes can be used, i.e., where thealkyl group is cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl andbranched and straight chain alkyl groups.

Other aldehydes useful in the production of the products of thisinvention include:

2-, 3- and 4-diphenylylcarboxaldehyde2,3,4-dimethoxydiphenylylcarboxaldehyde 2-, 3-, and4-azodiphenylylcarboxaldehyde 2-, 3-, and 4-oxydiphenylylcarboxaldehyde2-, 3-, and 4-iminodiphenylylcarboxaldehyde 2-, 3-, and4-methoxyoxydiphenylene-4'-carboxaldehyde 2-, 3-, and4-hexyloxyoxydiphenylene-4'-carboxaldehyde 2-, 3-, and4-methylthio-oxydiphenylene-4'-carboxaldehyde 2-, 3-, and4-dimethylamino-oxydiphenylene-4- carboxaldehyde 2-, 3-, and4-ethoxyoxydiphenylene-3-carboxaldehyde 2-, 3-, and4-ethylthiooxydiphenylene-3-carboxaldehyde 2-, 3-, and4-dimethylaminooxydiphenylene-3'- carboxaldehyde N-methyl-2-, 3- and4-iminodiphenylene-3'- carboxaldehyde N-propyl-2-, 3- and4-iminodiphenylene-4'- carboxaldehyde N-hexyl-2-, 3- and4-iminodiphenylene-4- carboxaldehyde N-n-propyl-2-, 3- and4-iminodiphenylene-4'-carboxaldehyde N-methyl-2-, 3-, and4-dimethylaminoiminodiphenylene- 3-carboxaldehyde 2-,h3-, and4-dimethylaminoazodiphenylene-4'-carboxaldeyde N,N-disubstitutedformamides used in the process of this invention can be readily preparedby the reaction of formic acid or methyl :t'ormate with a diamine.Included among the N,N-disubstituted formamides used to preparecompounds of this invention are N,N-di-n-hexyl- :formamide,N,N-dicyclophentylformamide, N,N-n-hexylcyclohexylformamide,N,N-phenylcyclohexylformamide, N,N-phenylethylformamide,N,N-phenylisopropylformamide and the like.

The aldehydes described above can be prepared as described in Wagner andZook, Synthetic Organic Chemistry, John Wiley and Sons, New York, 1953,pp. 279-315.

The following examples further illustrate the invention. Unlessotherwise indicated in the examples, parts are by weight. Pressures areatmospheric, and temperatures are in degrees centigrade.

EXAMPLE 1 p-Methoxy-a-trifluoromethylcinnamoyl fluoride To 13 g. ofanisaldehyde in a distilling flask was added 18 g. ofperfluoromethacrylyl fluoride. There was an exothermic reaction withevolution of gas. After this subsided, the product was distilled at 1mm. pressure to obtain 17.9 g. of p-rnethoXy-a-trifluoromethylcinamoylfluoride boiling at 86 C./l mm. This was washed with water andredistilled at 83 C./0.75 mm. The product was a colorless liquid, 111.5371.

Analysis.--Calcd. for C H F O (percent): C, 53.27; H, 3.25; F, 30.65.Found (percent): C, 53.56; H, 3.28; F, 30.13.

EXAMPLE 2 2-trifluoromethyl-3-dimethylaminoacryloyl fluoride To 89.0 g.(0.5 mole) of perfluoromethacrylyl fluoride, which was stirred in a drynitrogen atmosphere in a flask immersed in an ice bath, 36.5 g. (0.5mole) of dimethylformamide was added at a rate which maintained thereaction temperature at 12-15 (about one hour). The gas evolution wasimmediate and continuous during the addition. After the addition wascomplete (about one hour), the reaction mixture was stirred under a slowstream of nitrogen at room temperature for two hours and then distilledto give 74.5 g. of 2-trifluoromethyl-3-dimethylaminoacryloyl fluoride inthe form of a pale yellow liquid (81% yield),B.P. 67-68 C. (0.7 mm.).

The compound exhibited absorption in the infrared at 5.64 (GOP) and6.12 1. (C=C). The compound had the following maxima in the U.V.:

280m,u.(e 15,500) and ther Mm.

281 m (e 16,400). The F n.m.r. spectrum showed there were two isomerspresent in a 60:40 ratio. The main isomer showed absorption (relative totrichlorofluoromethane external standard) at 3,230 c.p.s. [CF doublet (J=I4 c.p.s.)] and at -1,470 c.p.s. [C01 quartet (J =I4 c.p.s.) intodoublets (J =7 c.p.s.)]. The minor isomer had absorption at +2,780C.p.S. (CF13, doublet (JCFS/COF=16 C.p-S.)) and at c.p.s. [COF, quartet(I cps =16 c.p.s.)].

The H n.m.r. showed two overlapping peaks centered at 6.751- (6H, N(CHof the two double bond isomers) and a doublet (J =7 c.p.s.) centered at2.5+ which overlapped with a broad band (1H).

Analysis.-Calcd. for C6H7F4NO (percent): C, 38.92; F, 41.05; H, 3.81; N,7.57. Found (percent): C, 39.42; F, 41.03; H, 3.92; N, 7.53.

EXAMPLE 3 5- (p-dimethylaminophenyl)-2-trifluoromethy1-2,4-

. pentadienoyl fluoride To a stirred suspension of p-dimethylaminocinnamaldehyde (17.0 g., 0.097 mole) in 80 ml. of ether, in a drynitrogen atmosphere, 18.0 g. (0.101 mole) of perfluoromethacrylylfluoride was added at rate to keep the reaction temperature between25-30. (No cooling was necessary.) After the addition was completed, thereaction mixture consisted of a deep red solution in which was suspendedred solid and some yellow solid (indicating unreacted aldehyde). Anadditional ml. of ether was added. Then 25 ml. of benzene was added mostof the solids dissolved) and the mixture was refluxed for two hoursuntil the evolved gases failed to smoke when they came in contact withpaper saturated with ammonia. The material was then concentrated invacuo to give 28.0 g. of 5 (p dimethylaminophenyl) 2 trifluoromethyl-2,4-pentadienoyl fluoride in the form of a violet solid, M.P. 96-105 0nrecrystallization from ether/hexane uycluhexuno max.

EtOH max.

The H n.m.r. spectrum had a singlet at 6.91- [6H, N(CH a doublet at3.31- (J=9.5 c.p.s., 2H) and a doublet at 2.451- (J :95 c.p.s.) whichoverlapped with a complex multiplet (total 5H). These latter absorptionscorrespond to an A B pattern of the four aromatic protons; the low fielddoublet overlaps with the vinyl protons. The F n.m.r. spectrum (relativeto trichlorofluoromethane internal standard) absorption at +3,470 c.p.s.(CF doublet, J =13.6 c.p.s. and 2,030 c.p.s. (COF complex pattern). Thesingle CF absorption showed this compound was a single isomerAnalysis.-Calcd. for C F H ON (percent): C, 58.52; F, 26.45; H, 4.57; N,4.88. Found (percent): C, 58.43; F, 26.47; H, 4.99; N, 4.84.

A sample of this material was recovered unchanged after refluxing inmethanol for a half hour.

EXAMPLE 4 p-Dimethylamino-a-trifluoromethylcinnamoyl fluoride To astirred suspension of 14.9 g. (0.1 mole) of p-dimethylaminobenzaldehydein ml. of ether in a dry nitrogen atmosphere, 19.0 g. (0.106 mole) ofperfluoromethacrylyl fluoride was added. The rate of addition wasadjusted to give a steady evolution of gas (COF and to maintain thereaction temperature between 2530 C. After the addition was completed(total time about two hours) all solids had dissolved and the solutionwas dark green. The solvent was removed with a rotary evaporator invacuo to give 26.0 g. of p-dimethylamino-u-trifluoromethylcinnamoylfluoride in the form of a yellow solid. This material was sublimed at0.15 mm. and 65 C. to give 24.0 g. (92%) of an analytically pure yellowsolid, M.P. 6269 C.

Analysis.Calcd. for C F H NO (M.W., 261.2) (percent): C, 55.18; F,29.10; H, 4.25; N, 5.37. Found (percent): C, 55.28; F, 29.12; H, 4.37;N, 5.71.

The compound exhibited absorption in the infrared (CHCl at 5.56; (C=O ofacid fluoride). The compound had the following maxima in the U.V.:

EtOH mnx.

The H n.m.r. absorption spectrum had absorption at 6.921- (6H singlet,N(CH at 3.47 (2H, doublet, J=l0 cps, aromatic H) and at 2.3-:- (doublet,J=l0 cps., aromatic H) which overlapped with a complex multiplet Theminor isomer had absorption at +3,230 cps [CF ('J =I3.8 cps.)] and atl,170 cps. [COF, quartet JCF3/COFZI3-8 CPS.) into doublets (Jco =2.2cps.)].

EXAMPLE 2-trifluoromethyl-3 Z-furyl -acryloyl fluoride A Carius tube wascharged at Dry Ice temperature with 35.6 g. (0.2 mole) ofperfluoromethacrylyl fluoride and 19.2 g. (0.2 mole) of furfural andsealed. After coming to room temperature, the reaction mixture consistedof a red homogeneous solution. This was left overnight at roomtemperature and then heated on the steam bath for three hours. The tubewas cooled in Dry Ice and opened to a liquid nitrogen trap to collect13.0 g. (98%) of carbonyl fluoride (IR, 5.141). The liquid remaining wasdistilled to give 24.0 g. (58%) of 2-trifiuoromethyl-3- (2-furyl)-acryloyl fluoride in the form of a pale green mobile liquid, B.P. 7478mm.), which absorbed in the infrared at 5.50 (COF). Repeateddistillation failed to remove the color. The compound had the followingmaxima in the U.V.:

cyclohexane max.

max.

332 I11/L(E18,100).

The F n.m.r. spectrum showed that there were two isomers present in a96:4 ratio. The main isomer showed absorption (relative totrichlorofluoromethane external standard) at +3,560 cps. [CF doublet (J=I3.6 cps.)] and -2,040 cps. [(COF, quartet (J =I3.6 cps.) into doublets(J =7.O cps.) into doublets (.IE) 0.7 cps.)]. The minor isomer hadabsorption -|-3,380 cps. [CF doublet (J =13.4 cps.)] and 1,180 cps.[COF, quartet (J =I3.4 cps.) into doublets (l :18 cps.)]. The H n.m.r.showed absorption at 3.31 [doublet (1:3.8 cps.) into doublets (1:1.8cps.) into doublets (150.6 cps.), 1H] and a complex multiplet centeredat 2.21 (3H).

Analysis.Calcd. for C H F O (percent: C, 46.17; H, 1.94; F, 36.52. Found(percent: C, 46.46; H, 2.09; F, 36.57.

EXAMPLE 6 2-trifluoromethyl-3- 3 -indolyl acryloyl fluoride To a stirredsuspension of indole-3-carboxaldehyde (14.5 g., 0.1 mole) in 60 ml. ofether, in a dry nitrogen atmosphere in a flask immersed in an ice bath,19.0 g. (0.107 mole) of perfluoromethacrylyl fluoride was added at arate to keep the temperature between 1520 C. and maintain a steadyevolution of gas. After the addition was completed, the reaction wasstirred for two hours at 40 C. and then concentrated in vacuo to give28.3 g. of 2-trifluoromethyl-3-(3-ind0lyl)acryloyl fluoride in the formof a yellow solid. The infrared spectrum in mineral oil showedabsorption at 3.0a (NH), 5.6 4 (COF). This product rapidly darkened. Itwas converted to the methyl ester by dissolving the total crude productin 50 ml. of methanol adding ml. of pyridine and stirring overnight. Thereaction was diluted with 100 ml. of methylene chloride and then washedconsecutively with water (1x 50 ml.), 10% HCl (2 50 ml.), water,saturated sodium bicarbonate (IX 50 ml.), and brine. The methylenechloride solution was dried over MgSO filtered, and concentrated invacuo to give 23.2 g. of methyl 2-trifluoromethyl-3-(3-indolyl)-acrylate in the form of an orange solid. A sample wasrecrystallized four times from cyclohexane/benzene and sublimed to givean analytical sample, M.P. 144.5- 145.5 C. The infrared spectrum (CHClhad absorption at 292 (N H), 3.39 1 and 3.51, (saturated C=H), 5.85(conj. ester C=O) 621 6.34 6.61 and 6.72 (conj. C=C, C=N and aromatic (CC) and strong absorption in the 8-10 1 region (C-F and a C-O). Thecompound had the following maxima in the U.V.:

351 ma (6 16,600), 275 ma (6 7,440), 264 ma (6 8,440), 218 m (6 24,700).

The F n.m.r. spectrum showed two CF groups (86: 14 ratio) correspondingto the cis-trans isomers. The major CF group appeared at +3,417 c.p.s.(trichlorofluoromethane internal standard) and the minor CF at +3,326cps. Each was split into doublet (J =1 cps). The H n.m.r. spectrumconsisted of a singlet at 6.131 (3H, CO CH a complex multiplet between2.1 and 2.81 (4H, aromatic H). a poorly resolved multiplet (possibly aquartet) at 2.01 (1H,

/CF CH=C a doublet at 1.371 (1H, 1:3 cps), and broad absorption centeredat 2.251 (1H, N-H).

Analysis.Calcd. for C H F NO (percent: C, 58.00; H, 3.75; F, 21.17; N,5.21. Found (percent): C, 58.33; H, 3.83; F, 20.88; N, 5.49.

EXAMPLE 7 2-trifluoromethyl-3- N-methyl-Z-pyrolyl) acryloyl fluoride To40.0 g. (0.225 mole) of perfluoromethacrylyl fluoride, which was stirredin a dry nitrogen atmosphere in a flask immersed in an ice bath, 21.8 g.(0.20 mole) of N- methylpyrrole-Z-carboxaldehyde was added at a ratewhich maintained the reaction temperature below C. (about one hour). Agentle stream of nitrogen was passed through the flask during the courseof the reaction to remove COF as it was formed. The reaction mixture wasconcentrated and the crude product was washed with hexane to give 32 g.(73%) of purple solid which was sublimed twice C. and 0.5 mm.) to give2-trifluoromethyl-3-(N-methyl-2-pyrro1yl)-acryloyl fluoride in the formof a yellow solid, M.P. 58-63 C.

The compound exhibited absorption in the infrared (KBr) at 5.62(conjugated C=O of COF) and 6.3 (conjugated C=C). The compound had thefollowing maxima in the U.V.:

EtOH Mm.

ksr glohcxano 365 I11,u.(e 28,500), 355 m (a 27,400).

The F n.m.r. spectrum showed that there were two isomers present in a76:24 ratio. The main isomer showed absorption (relative totrichlorofiuoromethane internal standard) at +3,500 c.p.s. [CF doublet(J =15.2 c.p.s.) into doublets (J =1.4 c.p.s.)] and at 1,887 c.p.s.[COF, quartet (J =15.2 c.p.s.) into doublets (J o =7-4 c.p.S.) intodoublets (JCQF/H2ZI-Z C-P-SJ]. The minor isomer had absorption at +3,419c.p.s. [C1 doublet (J =14.6 c.p.s.) into doublets c.p.s.) into doublets(J =O.7 c.p.s.)] and at 1,033 c.p.s. [COF, quartet (J =14.6 c.p.s.) intodoublets (J =2.4 c.p.s.)]

The H n.m.r. spectrum (CDCl showed a singlet at 6.251 (3H, NCH a doubletinto doublets at 3.651 (1H, 1 :48 c.p.s., J =2.6 c.p.s., 1 :06 c.p.s.)and complex poorly resolved absorption between 21 and 31 (3H).

Analysis.-Calcd. for C H F NO (percent): C, 48.88; H, 3.19; F, 34.37; N,6.34. Found (percent): C, 49.65, 49.52; H, 3.37, 3.27; F, 34.18; N,6.59.

EXAMPLE 8 Z-trifluoromethylcinnamoyl fluoride A Carious tube was chargedwith 42.0 g. of benzaldehyde (0.4 mole) and 36.0 g. ofperfluoromethacrylyl fluoride and heated in 150 C. for 40 hours. Thetube was then cooled in solid carbon dioxide and opened. The gases werevented and the product distilled to obtain 13.8 g. of crude2-trifluoromethylcinnamoyl fluoride in the form of a colorless liquid.The first 9.1 g. boiled at 110-122 C. at 18 mm. pressure and the lastTABLE (B) Procedure of (A) Aldehyde employed Example (C) Productobtained l-naphthaldehyde 2-naphthaldehyde 2-thiophenecarboxaldehyde 10p-(p-Dimethylaminophenylazo)benzaldehyde 11. p-Methylthiobenzaldehyde 124-0Xazolecarboxaldehyde 13 fi-isoxaz olecarboxaldehyde 14...-4-thiazolecarboxaldehyde 15.. 4-1m1dazoleearboxaldehyde 16.. 1,2,3triazoie-4-carboxaldehyd 17.. BenzofurfuraL;

18. 2-thianaphthenerarboxaldehyde- 19 p-Phenoxyhenzaldehyde 20p-(N-mcthyl-N-phenylamiuo) benzaldehyde 21--. 2-thiazolecarboxyaldehyde22. 1-methyl-2-benzimidazolecarboxaldehyde 23 240cmoxazolecarboxaldehyde24.-.. 2-benzothiazolecarboxaldehyde mv-Acnoomcncnmcnmoicnwvioomoowoooomw 4.7 g. boiled at 85-87 C. at 5 mm. pressure. Thisproduct was separated into its cis and trans isomers by gaschromatography. The infrared spectrum of the first isomer showedabsorption (CCl M5511. (conjugated COF) and 6.12 (conjugated C=C). Thecompound had the following maxima in the U.V.:

oyclohexane XTIDX 282 me (e 10,200), 220 m (6 6,800)

EtOH The F n.m.r. spectrum consisted of single CF and COF resonanceswhich showed that this product was one isomer. The CF resonance,centered at +3,670 c.p.s. (relative to trichlorofluoromethane), was adoublet (J.co =9.5 c'P-S.) into doublets c.p.s.); the COF resonance,centered at -2,350 c.p.s., was a quartet (J =9.S c.p.s.) into doublets(J =S.4 c.p.s.). The H n.m.r. showed a sharp peak at 2.557 (5H, aromaticH) and a doublet (.T =S.9 c.p.s.) into overlapping quartets (J =1.6c.p.s.) centered at 2.231 (1H, vinyl H). (These coupling constantsshould be :03 c.p.s.)

Analysis.-Calcd. for C H OF (M.W., 218.1) (percent): C, 55.06; H, 2.77;F, 34.84. Found (percent): C, 55.36; H, 2.84; F, 34.88.

The infrared spectrum of the second isomer showed absorption (CCl at5.5a (COF) and 6.12 (C=C) and differed from the other isomer in theregion between 79,u.. The F n.m.r. spectrum (CDCl relative to Freon 11external) showed a CF group at +3,321 c.p.s. [doublet (J =11.0 c.p.s.)]and COF group at 1,381 c.p.s. [quartet (J :110 c.p.s.)]. The H n.m.r.showed a sharp peak (external TMSi) at 2.551- (SH, aromatic H) andabsorption at 1.71 (1H, vinyl H).

xisooctane HUXX.

3-substituted 2 trifiuoromethylacryloyl fluorides are useful aswaterproofing agents for various papers and cellulosic materials. Someof these compounds are also useful as dyes for fibers and fabricscomposed of silk, wool, cellulose acetate, and nylon.

These uses are further illustrated in the examples below. I

EXAMPLE A Two strips of filter paper (1 sq. in.) were each treated with10 drops of a 50% solution of 2-trifluoromethyl-3- dimethylaminoacryloylfluoride in ether. The papers were dried. One strip was additionallytreated with three drops of a 50% solution of pyridine in ether. Afterdrying, the paper was covered with a glass plate and heated on a hotplate at -85 C. for 1015 minutes and then cooled to room temperature.When drops of water were placed on the treated papers, both showedstrong resistance to absorption of the water, whereas an untreated stripof filter paper absorbed a drop of water immediately. This procedure wasrepeated with identical results using p-dimethylamino 2trifiuoromethylcinnamoyl fluoride in place of 2-trifluoromethyl 3dimethylaminoacryloyl fluoride.

Compounds of Formula I containing p-dialkylaminophenyl groups are usefulas dyes. This is illustrated as follows:

EXAMPLE B To a solution of 0.030 g. ofp-dimethylamino-2-trifluoromethylcinnamoyl fluoride, swatches ofcellulose acetate, 66 nylon, silk and wool fabrics were added. Then asolution of 3 ml. of an 0.1% aqueous solution of a sulfonated lignindispersant in 10 ml. of water was added. The mixture was warmed at about60 C. for five minutes and then allowed to stand overnight at roomtemperature. The swatches were washed with soap and water and rinseduntil the rinsings were colorless. When dry the cellulose acetate, 66nylon, silk and wool swatches were all dyed yellow.

EXAMPLE C To a solution of 0.05 g. ofp-dimethylamino-2-trifluoromethylcinnamoyl fluoride in 10 ml. of benzeneand 10 1 1 ml. of pyridine a 2-inch square of cotton broadcloth wasadded. The mixture was heated under reflux for 24 hours. The cloth waswashed with soap and water and then with acetone until the acetonewashings were colorless. The dried fabric was dyed lemon yellow.

EXAMPLE D To a solution of 0.050 g. ofp-dimethylamino-2-trifluoromethyl-2,4-pentadienoyl fluoride in 18 ml. ofethanol containing swatches of cellulose acetate, 66 nylon, silk andwool fabrics was added a solution of 3 ml. of an 01% aqueous solution ofa sulfonated lignin dispersant in 12 ml. of water. The mixture washeated for five minutes at about 60 C. and then allowed to standovernight at room temperature. The swatches were washed and dried as inExample B. They were all dyed orange.

The foregoing detailed description has been given for clarity ofunderstanding only and no unnecessary limitations are to be understoodtherefrom. The invention is not limited to the exact details shown anddescribed, for obvious modifications will be apparent to those skilledin the art.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A compound of the formula wherein Z is a monovalent radical selectedfrom the group consisting of and CH: CH

12 dimethylaminophenyl)-a-trifluoromethyl 2,4 pentadienoyl fluoride.

4. The compound of claim 1 wherein Z is p-dimethylaminophenyl; saidcompound being p-dimethylamino-atrifluoromethylcinnamoyl fluoride.

5. The compound of claim 1 wherein Z is phenyl; said compound beingot-trifluoromethylcinnamoyl fluoride.

6. A process for preparing a compound of the formula H (31m 2 J=CC o Fwhich comprises reacting perfluoromethacrylyl fluoride with a formylcompound of the formula ZCHO, where Z is a monovalent radical selectedfrom the group consisting of and References Cited FOREIGN PATENTS11/1970 England 260239 1/1969 England 26080.8

LORRAINE A. WEINBERGER, Primary Examiner E. J. GLEIMAN, AssistantExaminer US. Cl. X.R.

